KR20140020721A - Electrophotographic photoreceptor, process cartridge, and image forming apparatus - Google Patents

Abstract

An object of this invention is to provide the electrophotographic photosensitive member which suppresses peeling of the layer formed on the electroconductive base.
As a means for solving such a problem, the electron which consists of a metal or an alloy, and has the cylindrical conductive base 1 whose average area of a crystal grain is 100 micrometer <^2> or more, and the photosensitive layer 3 provided on the conductive base 1 Provide a photosensitive member.

Description

ELECTROPHOTOGRAPHIC PHOTORECEPTOR, PROCESS CARTRIDGE, AND IMAGE FORMING APPARATUS}

The present invention relates to an electrophotographic photosensitive member, a process cartridge, and an image forming apparatus.

BACKGROUND ART An electrophotographic image forming apparatus has a high speed and high quality factor, and is used in image forming apparatuses such as copiers and laser beam printers. As a photoconductor used in an image forming apparatus, an organic photoconductor using an organic photoconductive material is the mainstream. When manufacturing an organic photosensitive member, for example, an undercoat layer (sometimes referred to as an intermediate layer) is formed on an aluminum substrate, and then a photosensitive layer composed of a photosensitive layer, in particular a charge generating layer and a charge transporting layer, may be formed. many.

For example, Patent Document 1 describes a method of manufacturing an image retainer having a thin cylindrical substrate having flexibility and an image retaining layer formed on the surface of the substrate. The process of obtaining a normal body by the impact process of forming a billet whole body in a thin cylindrical shape by giving a shock, The process of cut | disconnecting both ends of the normal body obtained by this process, and obtaining the said base material, A step of gripping an end portion on the side opposite to the side on which the billet is disposed at the time of impact processing of the substrate obtained by the step, and immersing the substrate in the paint for forming an upper layer layer to form an upper layer on the surface of the substrate. The manufacturing method of the phase holder which has a "is disclosed.

In addition, Patent Document 2 discloses a "thin flexible cylindrical image carrier having a flexible cylindrical substrate having a flexibility, an image bearing layer formed on the surface of the substrate, and the surface of the image bearing member. An image forming apparatus having an image forming process member that abuts on a substrate, wherein the substrate of the image carrier is a substrate formed by impact processing for forming the slug whole body in a thin cylindrical shape by impacting the slug with a punch. And the image forming apparatus in which the axial center portion of the image forming process member is shifted to the opposite side to the side on which the slug is disposed at the time of impact processing of the substrate with respect to the axial center portion of the substrate. It is.

In addition, Patent Document 3 discloses, "In the electrophotographic photosensitive member having a charge generating layer and a charge transporting layer on a conductive base, the surface of the base is a non-cutting cylindrical gas, and the charge generating layer has at least two layers. The electrophotographic photosensitive member which consists of a laminated structure of "," and the "electrophotographic photosensitive member using the base on which the surface finishing by the fine drawing process was performed" is disclosed.

Japanese Patent Application Laid-Open No. 2000-010306 Japanese Patent Application Laid-Open No. 11-352836 Japanese Patent Application Laid-Open No. 07-239562

An object of the present invention is to provide an electrophotographic photosensitive member which suppresses peeling of a layer formed on a conductive base.

The said subject is solved by the following means. In other words,

The invention according to claim 1,

A cylindrical conductive base composed of a metal or an alloy and having an average area of crystal grains of 100 µm ² or more,

Photosensitive layer provided on the conductive base

Electrophotographic photosensitive member having a.

The invention according to claim 2,

The electrophotographic photosensitive member of claim 1, wherein an average area of the crystal grains of the conductive base is 400 μm ² or more.

The invention according to claim 3,

The electrophotographic photosensitive member according to claim 1, wherein an average area of the crystal grains of the conductive base is 1400 µm ² or less.

The invention according to claim 4,

The electrophotographic photosensitive member of Claim 1 which has an undercoat layer provided between the said electroconductive base and the said photosensitive layer.

The invention according to claim 5,

The electrophotographic photosensitive member of Claim 4 in which the said undercoat layer contains the metal oxide particle surface-treated with the binder resin and the coupling agent which has an amino group.

The invention according to claim 6,

The electrophotographic photosensitive member of Claim 1 whose thickness of the said electroconductive base is 0.3 mm or more and 0.7 mm or less.

The invention according to claim 7,

The electrophotographic photosensitive member of Claim 1 whose thickness of the said electroconductive base is 0.4 mm or more and 0.6 mm or less.

The invention according to claim 8,

The electrophotographic photosensitive member according to claim 1, wherein the metal or alloy constituting the conductive base is aluminum or an aluminum alloy.

The invention according to claim 9,

The electrophotographic photosensitive member of claim 8, wherein an average area of the crystal grains of the conductive base is 400 μm ² or less.

The invention according to claim 10,

The electrophotographic photosensitive member according to claim 8, wherein an average area of the crystal grains of the conductive base is 1400 µm ² or less.

The invention according to claim 11,

The electrophotographic photosensitive member of Claim 8 which has an undercoat layer provided between the said electroconductive base and the said photosensitive layer.

The invention according to claim 12,

The electrophotographic photosensitive member of Claim 11 in which the said undercoat layer contains the metal oxide particle surface-treated with the binder resin and the coupling agent which has an amino group.

The invention according to claim 13,

The electrophotographic photosensitive member of Claim 8 whose thickness of the said electroconductive base is 0.3 mm or more and 0.7 mm or less.

The invention according to claim 14,

The electrophotographic photosensitive member of Claim 8 whose thickness of the said electroconductive base is 0.4 mm or more and 0.6 mm or less.

The invention according to claim 15,

The electrophotographic photosensitive member of Claim 8 whose content rate of aluminum of the said conductive bases is 99.5% or more.

The invention according to claim 16,

The electrophotographic photosensitive member of any one of Claims 1-15 is provided,

A process cartridge detachably attached to an image forming apparatus.

The invention according to claim 17,

The electrophotographic photosensitive member according to any one of claims 1 to 15,

Charging means for charging the surface of the electrophotographic photosensitive member;

Electrostatic latent image forming means for forming an electrostatic latent image on the surface of said electrophotographic photosensitive member,

Developing means for developing a latent electrostatic image formed on the surface of said electrophotographic photosensitive member with toner to form a toner image;

Transfer means for transferring a toner image formed on the surface of the electrophotographic photosensitive member onto a recording medium

An image forming apparatus having a.

According to the invention of Claims 1-3, the electrophotographic photosensitive member which suppresses peeling of the layer formed on the conductive base is provided, compared with the case where the average area of the crystal grains of the conductive base is less than 100 µm ² .

According to invention of Claim 4, the electrophotographic photosensitive member which suppresses peeling of an undercoat layer is provided compared with the case where the average area of the crystal grain of a conductive base is less than 100 micrometer <^2> .

According to invention of Claim 5, the electrophotographic photosensitive member which suppresses corrosion of an electroconductive gas is provided compared with the case where metal oxide particle is not surface-treated with the coupling agent which has an amino group.

According to the invention according to claim 6 or 7, the electrophotographic which suppresses the peeling of the layer formed on the conductive base even when the thickness of the conductive base is as thin as the above range, compared with the case where the average area of the crystal grains of the conductive base is less than 100 µm ^2. A photosensitive member is provided.

According to the invention of Claims 8-10, the electrophotographic photosensitive member which suppresses peeling of the layer formed on the conductive base compared with the case where the average area of the crystal grain of the conductive base which is aluminum or an aluminum alloy is less than 100 micrometer <^2> is provided.

According to the invention according to claim 11, an electrophotographic photosensitive member which suppresses peeling of the undercoat layer is provided as compared with the case where the average area of the crystal grains of the conductive base which is aluminum or an aluminum alloy is less than 100 µm ² .

According to invention of Claim 12, the electrophotographic photosensitive member which suppresses corrosion of an electroconductive gas is provided compared with the case where metal oxide particle is not surface-treated with the coupling agent which has an amino group.

According to the invention according to claim 13 or 14, an electrophotograph which suppresses peeling of the layer formed on the conductive base even when the thickness of the conductive base is as thin as the above range, compared to the case where the average area of the crystal grains of the conductive base is less than 100 µm ^2. A photosensitive member is provided.

According to invention of Claim 15, the electrophotographic photosensitive member which can suppress generation | occurrence | production of an image defect is provided, compared with the content rate of aluminum of a conductive base less than 99.5%.

According to the invention according to claim 16, the process of suppressing an image defect due to peeling of a layer formed on the conductive base of the electrophotographic photosensitive member, as compared with the case of having an electrophotographic photosensitive member having an average area of crystal grains of the conductive substrate of less than 100 µm ^2. A cartridge is provided.

According to the invention according to claim 17, an image in which an image defect due to peeling of a layer formed on a conductive base of an electrophotographic photosensitive member is suppressed, compared with a case in which an electrophotographic photosensitive member having an average area of crystal grains of the conductive substrate is less than 100 µm ^2. A forming apparatus is provided.

1 is a schematic view showing an example of a layer structure of an electrophotographic photosensitive member according to the present embodiment.
2 is a schematic view showing another example of the layer structure of the electrophotographic photosensitive member according to the present embodiment.
3 is a schematic view showing another example of the layer structure of the electrophotographic photosensitive member according to the present embodiment.
4 is a schematic view showing another example of the layer structure of the electrophotographic photosensitive member according to the present embodiment.
5 is a schematic view showing another example of the layer configuration of the electrophotographic photosensitive member according to the present embodiment.
6 is a schematic view showing another example of the layer configuration of the electrophotographic photosensitive member according to the present embodiment.
7 is a schematic configuration diagram showing an image forming apparatus according to the present embodiment.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment which is an example of this invention is described.

<Electrophotographic photosensitive member>

The electrophotographic photosensitive member (hereinafter sometimes referred to simply as "photosensitive member") according to the present embodiment has a conductive base and a photosensitive layer provided on the conductive base.

The conductive base is a cylindrical conductive base composed of a metal or an alloy and having an average area of crystal grains of 100 µm ² or more.

In the electrophotographic photosensitive member according to the present embodiment, peeling of a layer (for example, an undercoat layer and a photosensitive layer) formed on the conductive substrate is suppressed by the above configuration.

Although the reason is not clear, it can be considered that it is based on the reason shown below.

Cylindrical conductive bases composed of metals or alloys may plastically deform under the influence of heating. When the conductive base is plastically deformed, the layer (for example, the undercoat layer or the photosensitive layer itself) formed on the conductive base easily peels off.

In particular, reducing the thickness of the cylindrical conductive substrate made of a metal or an alloy is advantageous from the viewpoint of reducing the weight of the electrophotographic photosensitive member or the image forming apparatus (or process cartridge) including the same or reducing the cost, for example. When the thickness of the conductive base is reduced, the conductive base is easily plastically deformed, and the layer (for example, the undercoat layer or the photosensitive layer itself) formed on the conductive base is easily peeled off.

On the other hand, it is thought that peeling of the layer formed in the electroconductive base is suppressed by making the average area of the crystal grain of a conductive base into the said range. It is considered that this is because by increasing the average area of the crystal grains in the above range, the individual crystal grains become large, the plastic strain decreases, and the elastic strain increases.

For this reason, in the electrophotographic photosensitive member which concerns on this embodiment, it can be considered that peeling of the layer (for example, an undercoat layer and the photosensitive layer) formed on the malleable base is suppressed.

In particular, when an undercoat layer is provided between the conductive substrate and the photosensitive layer, the thickness of the undercoat layer is thinner than that of the photosensitive layer, and the peeling easily occurs when the conductive base is plastically deformed. In this embodiment, since plastic deformation of an electroconductive base is suppressed, peeling of the said undercoat layer becomes easy to be suppressed.

Moreover, when providing the undercoat layer containing a binder resin and the metal oxide particle surface-treated with the coupling agent which has an amino group as this undercoat layer, it oxidizes with the coupling agent which has the said amino group, and advances corrosion of an electroconductive gas. It becomes easy to do it. However, in this embodiment, the corrosion of the conductive base is easily suppressed. It is considered that this is because, when the average area of the crystal grains of the conductive base is in the above range, the seam (grain boundary) between the crystal grains that is likely to cause oxidation is reduced.

EMBODIMENT OF THE INVENTION Hereinafter, the electrophotographic photosensitive member which concerns on this embodiment is demonstrated, referring drawings.

1-6 is schematic which shows the example of the laminated constitution of the photosensitive member which concerns on this embodiment. The photoconductor shown in FIG. 1 is comprised from the electroconductive base 1, the undercoat layer 2 formed on the electroconductive base 1, and the photosensitive layer 3 formed on the undercoat layer 2. As shown in FIG.

As shown in FIG. 2, the photosensitive layer 3 may have a two-layer structure of the charge generating layer 31 and the charge transporting layer 32. 3 and 4, the protective layer 5 may be provided on the photosensitive layer 3 or on the charge transport layer 32. 5 and 6, the intermediate layer 4 may be provided between the undercoat layer 2 and the photosensitive layer 3 or between the undercoat layer 2 and the charge generating layer 31.

In addition, although the intermediate | middle layer 4 has shown the aspect provided between the undercoat layer 2 and the photosensitive layer 3, or between the undercoat layer 2 and the charge generation layer 31, the electroconductive base 1 and the undercoat layer ( You may provide in between 2). Of course, the sun which does not provide the intermediate | middle layer 4 may be sufficient.

Next, each element of the electrophotographic photosensitive member will be described. In addition, description is abbreviate | omitted.

(Conductive gas)

A conductive substrate is, in view of that in an average area of ² or more of the crystal grains 100㎛ viewpoint of suppressing the exfoliation of the layer formed on the conductive substrate, and the corrosion resistance of the conductive substrate, preferably 200㎛ ² or more, and more preferably Is 400 µm ² or more. The upper limit of the average area of the crystal grains is preferably 1400 μm ² (preferably 2000 μm ² or less) from the viewpoint of the manufacturing constraints.

The measuring method of the average area of a crystal grain is as follows.

First, the layer (photosensitive layer etc.) formed on the outer peripheral surface of electroconductive base is removed from the photosensitive member by a cutter etc., or melt | dissolved and removed by a solvent etc.

Next, the sample obtained from the electroconductive base from which the layer formed on the outer peripheral surface was removed was carried out by grinding | polishing with a grinding | polishing machine after epoxy resin embedding as follows. First, polishing was performed using water-resistant abrasive paper # 500, and then mirror-finished by buff polishing, and the cross section of the conductive base was observed and measured by VE SEM manufactured by KEYENCE.

Specifically, the sample was produced for four locations (total 4 × 3 = 12 locations) every 90 degrees in the circumferential direction at a position of 5 mm from the both ends of the axial direction of the conductive base and the axial center of the conductive base.

Image processing in which VE SEM made by KEYENCE is standardly equipped with the area of one crystal grain which exists in the position corresponding to the range of 30 micrometers x 20 micrometers of axial directions from the outer peripheral surface of a base | substrate of each sample. Obtained by software, the area of the crystal grains of 12 samples is number-averaged, and this is obtained as the average area of the crystal grains of the conductive base.

The conductive base is composed of a metal or an alloy. Specifically, it consists of metals or alloys, such as aluminum, copper, magnesium, silicon, zinc, chromium, nickel, molybdenum, vanadium, indium, gold, platinum, stainless steel, etc., for example. In addition, "conductive" means that the volume resistivity is less than 10 ¹³ Ωcm.

Among these, as an electroconductive base, the aluminum base is mentioned suitably, for example.

In particular, a base made of aluminum having a purity (aluminum content rate) of 90% or more (preferably 95% or more, more preferably 99.5% or more) can obtain the flexibility of the gas, and thus the electrophotographic photosensitive member in the image forming process. It is easy to receive the action of a member more uniformly from the member to contact (for example, the charging member of a contact system), and it becomes easy to obtain the target image.

The conductive base may be cylindrical in shape, and may be any of drum and belt.

Although the outer diameter of an electroconductive support body does not have a restriction | limiting in particular, It is good to set it as 30 mm or less. When the outer diameter is 30 mm or less, dimensional stability can be easily secured even if the purity (aluminum content) is made of flexible aluminum such as 90% or more.

Although the thickness of an electroconductive support body does not have a restriction | limiting in particular, It is good that they are 0.3 mm or more and 0.7 mm or less (preferably 0.4 mm or more and 0.6 mm or less). Even if thickness is thinned in the said range, peeling of the layer formed on an electroconductive base is suppressed.

The conductive base can be obtained by, for example, forming a metal or alloy ingot (ingot) into a cylindrical shape by extrusion. In addition, the conductive base is ironed on the obtained cylindrical molded body after forming a metal or alloying material (hereinafter sometimes referred to as "slug") into a cylindrical shape by impact press working. You may obtain it by making it into the cylindrical molded object of the thickness made into the objective by processing. After the impact press working, the cylindrical molded product may be subjected to drawing and then ironed.

And in order to obtain the electroconductive base which has the average area of the crystal grain of the said range, for example, the homogenization process conditions (heating process conditions: temperature, processing time) of a metal or alloy ingot or slug, the rolling conditions at the time of slug preparation And conditions for processing (the number of times of drawing or ironing), and annealing treatment conditions (temperature, processing time) of the cylindrical molded body after processing, and the like.

In addition, the average area of crystal grains tends to increase as the ingot and the slug homogenization treatment and annealing treatment are performed for a long time at a high temperature. Moreover, as rolling, extrusion molding, or ironing are performed, the average area of the crystal grains tends to decrease.

In addition, the conductive base may be subjected to a process such as mirror cutting, etching, anodic oxidation, roughening, centerless grinding, sandblasting, wet honing, or the like beforehand.

In addition, when the electrophotographic photosensitive member is used in a laser printer, the surface of the conductive base is roughened to 0.04 µm or more and 0.5 µm or less in the centerline average roughness Ra in order to prevent interference caused when irradiating laser light. It is preferable to make it. If Ra is less than 0.04 µm, the surface is close to a mirror surface, and thus the interference prevention effect tends to be insufficient. If Ra exceeds 0.5 µm, the image quality tends to be rough even when a film is formed. In addition, when non-interfering light is used for the light source, roughening of the interference protection is not particularly necessary, and generation of defects due to irregularities on the surface of the conductive substrate can be prevented, which is suitable for longer life.

(Undercoat layer)

The undercoat layer is comprised containing binder resin, metal oxide particle, and an electron accepting compound as needed.

· Binder Resin

As a binder resin, acetal resin (for example, polyvinyl butyral etc.), polyvinyl alcohol resin, casein, a polyamide resin, a cellulose resin, gelatin, a polyurethane resin, a polyester resin, a methacryl resin, an acryl Polymer resin compounds such as resins, polyvinyl chloride resins, polyvinylacetate resins, vinyl chloride-vinyl acetate-maleic anhydride resins, silicone resins, silicone-alkyd resins, phenol resins, phenol-formaldehyde resins, melamine resins, and the like. Can be.

Metal oxide particles

Examples of the metal oxide particles include particles such as antimony oxide, indium oxide, tin oxide, titanium oxide, and zinc oxide.

Among these, as the metal oxide particles, particles of tin oxide, titanium oxide, and zinc oxide are preferable from the viewpoint of the stability of the electrical properties.

As the metal oxide particles, a conductive powder having a particle size of preferably 100 nm or less, particularly 10 nm or more and 100 nm or less can be preferably used. The particle size here means an average primary particle size. The average primary particle diameter of a metal oxide particle is a value observed and measured by SEM (scanning electron microscope).

When the particle diameter of the metal oxide particles is 10 nm or less, the surface area of the metal oxide particles increases, and the uniformity of the dispersion may decrease. On the other hand, when the particle diameter of the metal oxide particles exceeds 100 nm, the secondary particles or higher order particles are expected to have a particle diameter of about 1 μm, and the metal oxide particles do not exist in the undercoat layer. It becomes easy to become a partial, what is called a sea island structure, and the image quality defect, such as the nonuniformity of a halftone density, may arise, for example.

As the metal oxide particles is preferably in a powder (粉體) resistance of less than 10 ⁴ Ω · ㎝ more than ¹⁰ 10 Ω · ㎝. Thereby, it becomes easy to realize that an undercoat layer obtains an appropriate impedance at the frequency corresponding to the electrophotographic process speed.

When the resistance value of the metal oxide particles is lower than 10 ⁴ Ω · cm, the slope of the particle addition amount dependency of the impedance is too large, which may make it difficult to control the impedance. On the other hand, when the resistance value of the metal oxide particles is higher than 10 ¹⁰ Ω · cm, the residual potential may increase.

It is preferable that the metal oxide particle is surface-treated with at least 1 type of coupling agent as needed for the purpose of the improvement of agent characteristics, such as dispersibility.

As a coupling agent, it is good that it is at least 1 sort (s) chosen from a silane coupling agent, a titanate coupling agent, and an aluminate coupling agent. Among these, the coupling agent which has an amino group is suitable from a viewpoint of the broking function in the interface of an undercoat layer and a photosensitive layer (for example, a charge generation layer), and the resistance adjustment function of an undercoat layer.

Examples of specific coupling agents include vinyltrimethoxysilane, 3-methacryloxypropyl-tris (2-methoxyethoxy) silane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycol Cidoxypropyltrimethoxysilane, vinyltriacetoxysilane, 3-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N, N-bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, and the like. Silane coupling agent, aluminate-based coupling agents such as acetoalkoxy aluminum diisopropylate, isopropyl triisostearoyl titanate, bis (dioctylpyrophosphate), isopropyl tri (N-aminoethyl-aminoethyl) Titanate coupling agents, such as titanate, etc. are mentioned, Not to be constant. In addition, you may use these coupling agents in mixture of 2 or more type.

It is preferable that the processing amount of a coupling agent is 0.1 mass% or more and 3 mass% or less with respect to a metal oxide particle, Preferably they are 0.3 mass% or more and 2.0 mass% or less, More preferably, they are 0.5 mass% or more and 1.5 mass% or less.

In addition, the throughput of a coupling agent is measured as follows.

There are analytical methods such as the FT-IR method, 29Si solid NMR method, thermal analysis, and XPS, but the FT-IR method is the simplest. In the FT-IR method, the usual KBr purification method or the ATR method may be used. The throughput of the coupling agent is measured by mixing a small amount of treated metal oxide particles with KBr and measuring FT-IR.

The metal oxide particles may be subjected to a heat treatment after the surface treatment with the coupling agent in order to improve the environmental dependence of the resistance value and the like, if necessary. As for heat processing temperature, 150 degreeC or more and 300 degrees C or less, for example, processing time are 30 minutes or more and 5 hours or less are good.

30 mass% or more and 60 mass% or less are preferable, and, as for content of a metal oxide particle, 35 mass% or more and 55 mass% or less are more preferable.

Electron-soluble compound

The electron-accepting compound is a material that chemically reacts with the surface of the metal oxide particles contained in the undercoat layer, or a material that adsorbs to the surface of the metal oxide particles, and may be selectively present on the surface of the metal oxide particles.

As the electron-accepting compound, an electron-accepting compound having an acidic group is applied. As this acidic group, a hydroxyl group (phenol hydroxyl group), a carboxy group, a sulfonyl group, etc. are mentioned.

Specific examples of the electron-accepting compound include quinone, anthraquinone, coumarin, phthalocyanine, triphenylmethane, anthocyanin, flavone, flaren, ruthenium complex, xanthene, benzoxazine and porphyrin. The compound of the type | system | group is mentioned.

In particular, the electron-accepting compound is preferably an anthraquinone-based material (anthraquinone derivative) in consideration of ghost suppression and safety, availability, and electron transport ability of the material, and is particularly represented by the following general formula (1). Preferred are those compounds.

In general formula (1), n1 and n2 respectively independently represent the integer of 1 or more and 3 or less. m1 and m2 represent the integer of 0 or 1 each independently. R ¹ and R ² each independently represent an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms.

Moreover, as an electron accepting compound, the compound represented by following General formula (2) may be sufficient.

In general formula (2), n1, n2, n3, and n4 respectively independently represent the integer of 1 or more and 3 or less. m1 and m2 represent the integer of 0 or 1 each independently. r represents an integer of 2 or more and 10 or less. R ¹ and R ² each independently represent an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms.

Here, in general formula (1) and (2), as a C1-C10 alkyl group which R <^1> and R <^2> represent, any of a linear or pulverized phase may be sufficient, For example, a methyl group, an ethyl group, A propyl group, an isopropyl group, etc. are mentioned. As a C1-C10 alkyl group, Preferably they are 1 or more and 8 or less alkyl groups, More preferably, they are 1 or more and 6 or less alkyl groups.

The alkoxyl group (alkoxyl group) having 1 to 10 carbon atoms represented by R ¹ and R ² may be either a straight chain or a pulverized phase, for example, a methoxy group, an ethoxy group, a propoxy group or isopropoxy. Season, etc. can be mentioned. As an alkoxy group of 1 or more and 10 or less carbon atoms, Preferably they are 1 or more and 8 or less alkoxy groups, More preferably, they are 1 or more and 6 or less alkoxy groups.

Although the specific example of an electron accepting compound is shown below, it is not limited to these.

The content of the electron-accepting compound is determined from the surface area and the content of the metal oxide particles of the metal oxide particles, which are the chemical reactions or adsorption partners, and the electron transporting ability of the respective materials. It is good and, More preferably, it is the range of 0.1 mass% or more and 10 mass% or less.

When content of an electron accepting compound is 0.1 mass% or less, it may be difficult to express the effect of an electron accepting compound. Conversely, when the content of the electron-accepting compound exceeds 20% by mass, it is easy to cause aggregation of the metal oxide particles, and the metal oxide particles tend to be uneven in the undercoating layer, and it becomes difficult to form a good conductive path. There is. Therefore, the residual potential rises, not only generating ghost but also generating black spots and unevenness of halftone concentrations.

Other additives

Resin particles are mentioned as other additives. When coherent light, such as a laser, is used for an exposure apparatus, it is good to prevent a moire. For that purpose, it is good to adjust the surface roughness of the undercoat layer to 1 / 4n (n is refractive index of an upper layer) or more and 1/2 or less of the exposure laser wavelength (lambda) used. Therefore, when resin particle is added to an undercoat layer, adjustment of surface roughness is implement | achieved. Examples of the resin particles include silicone resin particles, crosslinked polymethyl methacrylate (PMMA) resins, and the like.

Moreover, as another additive, it is not limited to the above, A well-known additive is also mentioned.

Formation of Undercoat Layer

At the time of formation of an undercoat layer, the coating liquid for undercoat layer formation which added the said component to the solvent is used. The coating liquid for undercoat layer formation can be obtained by disperse | distributing what pre-mixed or pre-dispersed an electron-accepting compound and other additives, for example to a metal oxide particle as needed in a binder resin.

As a solvent used for obtaining the coating liquid for forming an undercoat layer, the well-known organic solvent which melt | dissolves the above-mentioned binder resin, for example, alcohol type, aromatic type, halogenated hydrocarbon type, ketone type, ketone alcohol type, ether type, ester type Solvents may be mentioned. You may use these solvents individually or in mixture of 2 or more types.

A well-known dispersion method can be used as a method of disperse | distributing metal oxide particle to the coating liquid for undercoat layer formation. For example, a roll mill, a ball mill, a vibrating ball mill, an attritor, a sand mill, a colloid mill, a paint shaker, etc. are mentioned.

As a coating method of the coating liquid for undercoat layer formation, well-known coating methods, such as the dip coating method, the blade coating method, the wire bar coating method, the spray coating method, the bead coating method, the air knife coating method, and the curtain coating method, can be used.

It is preferable that the undercoat layer is 35 or more and 50 or less in Vickers hardness.

From the viewpoint of image ghost suppression, the thickness of the undercoat layer is preferably 15 µm or more, more preferably 15 µm or more and 30 µm or less, further preferably 20 µm or more and 25 µm or less.

(Middle layer)

An intermediate | middle layer is provided as needed between the undercoat layer and the photosensitive layer, for an electrical property improvement, an image quality improvement, an image quality retention improvement, the photosensitive layer adhesiveness improvement, etc., for example. In addition, you may provide an intermediate | middle layer between an electroconductive base and an undercoat layer.

As a binder resin used for an intermediate | middle layer, an acetal resin (for example, polyvinyl butyral etc.), polyvinyl alcohol resin, casein, a polyamide resin, a cellulose resin, gelatin, a polyurethane resin, a polyester resin, a methacryl resin, an acryl Zirconium, titanium, And organometallic compounds containing aluminum, manganese, silicon atoms and the like. You may use these compounds individually or as a mixture or polycondensate of several compounds. Especially, the organometallic compound containing zirconium or silicon is suitable from the point that the residual potential is low, there is little change of potential by an environment, and the change of potential by repeated use is small.

When the intermediate layer is formed, a coating liquid for forming an intermediate layer in which the above components are added to a solvent is used.

As the coating method for forming the intermediate layer, conventional methods such as dip coating, push-up coating, wire bar coating, spray coating, blade coating, knife coating and curtain coating can be used. have.

In addition to improving the coatability of the upper layer, the intermediate layer also serves as an electrical breaking layer. However, when the film thickness is too large, the electrical barrier may be too strong, resulting in an increase in dislocation or increase in dislocation due to repetition. . Therefore, when forming an intermediate | middle layer, it is good to set to the film thickness range of 0.1 micrometer or more and 3 micrometers or less. In addition, you may use the intermediate | middle layer in this case as an undercoat layer.

(Charge generation layer)

The charge generating layer is configured to contain a charge generating material and a binder resin, for example. In addition, the charge generating layer may be constituted by a vapor deposition film of a charge generating material.

Examples of the charge generating material include phthalocyanine pigments such as metal-free phthalocyanine, chlorogallium phthalocyanine, hydroxygallium phthalocyanine, dichlorotin phthalocyanine, and titanyl phthalocyanine. Chlorogallium phthalocyanine crystal having diffraction peaks strong at least 7.4 °, 16.6 °, 25.5 ° and 28.3 °, at least 7.7 °, 9.3 °, of Bragg angle (2θ ± 0.2 °) to CuKα characteristic X-ray Metal free phthalocyanine crystals having strong diffraction peaks at 16.9 °, 17.5 °, 22.4 ° and 28.8 °, at least 7.5 °, 9.9 °, 12.5 °, 16.3 °, of Bragg angle (2θ ± 0.2 °) for CuKα characteristic X-rays, Hydroxygallium phthalocyanine crystals having strong diffraction peaks at 18.6 °, 25.1 ° and 28.3 °, having diffraction peaks at least 9.6 °, 24.1 ° and 27.2 ° of Bragg angle (2θ ± 0.2 °) for CuKα characteristic X-ray Titanylphthalocyanine crystals . In addition, as a charge generating material, a quinone pigment, a perylene pigment, an indigo pigment, a bisbenzoimidazole pigment, anthrone pigment, a quinacridone pigment, etc. are mentioned. These charge generating materials may be used singly or in combination of two or more.

As binder resin which comprises a charge generating layer, polycarbonate resin, such as bisphenol A type or bisphenol Z type, an acrylic resin, methacryl resin, polyarylate resin, polyester resin, polyvinyl chloride resin, polystyrene resin, for example , Acrylonitrile-styrene copolymer resin, acrylonitrile-butadiene copolymer, polyvinylacetate resin, polyvinyl formal resin, polysulfone resin, styrene-butadiene copolymer resin, vinylidene chloride-acrylonitrile copolymer resin, Vinyl chloride-vinyl acetate-maleic anhydride resin, silicone resin, phenol-formaldehyde resin, polyacrylamide resin, polyamide resin, poly-N-vinylcarbazole resin and the like. You may use these binder resin individually or in mixture of 2 or more types.

In addition, the compounding ratio of the charge generating material and the binder resin is preferably in the range of 10: 1 to 1:10.

When forming the charge generation layer, a coating liquid for forming a charge generation layer to which the above components are added to a solvent is used.

As a method of disperse | distributing particle | grains (for example, a charge generating material) in the coating liquid for charge generation layer formation, media dispersers, such as a ball mill, a vibrating ball mill, an attritor, a sand mill, a horizontal sand mill, and stirring, are stirred. And medialess dispersers such as ultrasonic dispersers, roll mills, and high pressure homogenizers are used. Examples of the high-pressure homogenizer include a collision type in which a dispersion liquid is dispersed in a liquid-liquid collision or a liquid-wall collision under a high pressure, or a through-type dispersion in which a fine channel is dispersed through a high-pressure state.

Examples of the method for applying the coating liquid for charge generation layer formation on the undercoat layer include an immersion coating method, a push-up coating method, a wire bar coating method, a spray coating method, a blade coating method, a knife coating method and a curtain coating method. .

The film thickness of the charge generation layer is preferably set in the range of 0.01 μm to 5 μm, more preferably 0.05 μm to 2.0 μm.

(Charge transport layer)

The charge transporting layer contains a charge transporting material and, if necessary, a binder resin.

As the charge transport material, for example, oxadiazole derivatives such as 2,5-bis (p-diethylaminophenyl) -1,3,4-oxadiazole, 1,3,5-triphenyl-pyrazoline Pyrazoline derivatives such as 1- [pyridyl- (2)]-3- (p-diethylaminostyryl) -5- (p-diethylaminostyryl) pyrazoline, triphenylamine, N, N Aromatic tertiary amino compounds such as' -bis (3,4-dimethylphenyl) biphenyl-4-amine, tri (p-methylphenyl) aminyl-4-amine, dibenzylaniline, N, N'-bis ( Aromatic tertiary diamino compounds such as 3-methylphenyl) -N, N'-diphenylbenzidine, 3- (4'-dimethylaminophenyl) -5,6-di- (4'-methoxyphenyl) -1 1,2,4-triazine derivatives such as 2,4-triazine, hydrazone derivatives such as 4-diethylaminobenzaldehyde-1,1-diphenylhydrazone, 2-phenyl-4-styryl-quina Quinazoline derivatives such as sleepy, benzofuran derivatives such as 6-hydroxy-2,3-di (p-methoxyphenyl) benzofuran, p- (2,2-diphenylvinyl) -N, N-diphenyl Such as aniline carbazole derivatives such as α-stilbene derivatives, enamine derivatives and N-ethylcarbazole, hole transport materials such as poly-N-vinylcarbazole and derivatives thereof, quinone compounds such as chloranyl and bromoanthraquinone, Electrons such as fluorenone compounds such as tetracyanoquinomimethane compounds, 2,4,7-trinitrofluorenone, 2,4,5,7-tetranitro-9-fluorenone, xanthone compounds, and thiophene compounds The polymer etc. which have a transport material and the group which consists of said compound in a main chain or a side chain are mentioned. You may use these charge transport materials 1 type or in combination of 2 or more types.

Examples of the binder resin constituting the charge transport layer include polycarbonate resins such as bisphenol A type or bisphenol Z type, acrylic resins, methacryl resins, polyarylate resins, polyester resins, polyvinyl chloride resins, polystyrene resins, Acrylonitrile-styrene copolymer resin, acrylonitrile-butadiene copolymer resin, polyvinylacetate resin, polyvinyl formal resin, polysulfone resin, styrene-butadiene copolymer resin, vinylidene chloride-acrylonitrile copolymer resin, Insulating resins such as vinyl chloride-vinyl acetate-maleic anhydride resin, silicone resin, phenol-formaldehyde resin, polyacrylamide resin, polyamide resin, chlorine rubber, and polyvinylcarbazole, polyvinylanthracene, polyvinylpyrene, etc. And organic photoconductive polymers. You may use these binder resin individually or in mixture of 2 or more types.

Moreover, as for the compounding ratio of a charge transport material and the said binder resin, 10: 1-1: 5 are preferable, for example.

The charge transport layer is formed using the coating liquid for charge transport layer formation which added the said component to the solvent.

As a method of apply | coating the coating liquid for charge transport layer formation on a charge generating layer, conventional methods, such as an immersion coating method, the push-up coating method, the wire bar coating method, the spray coating method, the blade coating method, the knife coating method, the curtain coating method, etc. Can be used.

The film thickness of the charge transport layer is preferably set in the range of 5 占 퐉 to 50 占 퐉, and more preferably in the range of 10 占 퐉 to 40 占 퐉.

(Protective layer)

A protective layer is provided on the photosensitive layer as needed. The protective layer is further provided in order to prevent chemical change of the charge transport layer during charging or to improve the mechanical strength of the photosensitive layer, for example, in a photosensitive member having a laminated structure.

Therefore, it is good for the protective layer to apply the layer comprised containing the crosslinked material (hardened | cured material). As these layers, well-known structures, such as the reactive charge transport material and the hardened layer of the composition containing curable resin as needed, and the hardened layer which disperse | distributed the charge transport material in curable resin are mentioned, for example. Moreover, you may comprise the protective layer from the layer which disperse | distributed the charge transport material in binder resin.

A protective layer is formed using the coating liquid for protective layer formation which added the said component to the solvent.

As a method of coating the coating liquid for forming a protective layer on the charge generating layer, conventional methods such as an immersion coating method, a push-up coating method, a wire bar coating method, a spray coating method, a blade coating method, a knife coating method and a curtain coating method Can be used.

The film thickness of a protective layer becomes like this. Preferably it is 1 micrometer or more and 20 micrometers or less, More preferably, it is set in the range of 2 micrometers or more and 10 micrometers or less.

(Single layer photosensitive layer)

The single-layer photosensitive layer (charge generation / charge transport layer) contains a binder resin, a charge generation material, and a charge transport material, for example. These materials are the same as those described in the charge generating layer and the charge transport layer.

In the single-layer photosensitive layer, the content of the charge generating material is preferably 10% by mass or more and 85% by mass or less, more preferably 20% by mass or more and 50% by mass or less. Moreover, it is preferable to make content of a charge transport material into 5 mass% or more and 50 mass% or less.

The formation method of a single-layer photosensitive layer is the same as the formation method of a charge generation layer and a charge transport layer. 5 micrometers or more and 50 micrometers or less are preferable, and, as for the thickness of a single-layer photosensitive layer, it is more preferable to set it as 10 micrometers or more and 40 micrometers or less.

(etc)

In the electrophotographic photosensitive member according to the present embodiment, the photosensitive layer or the protective layer includes an antioxidant and a light in the photosensitive layer for the purpose of preventing deterioration of the photosensitive member due to ozone, an oxidizing gas generated in an image forming apparatus, or light and heat. You may add additives, such as a stabilizer and a heat stabilizer.

Further, at least one electron-accepting substance may be added to the photosensitive layer or the protective layer for the purpose of improving the sensitivity, reducing the residual potential, reducing fatigue during repeated use, and the like.

Moreover, you may add silicone oil as a leveling agent to the coating liquid which forms each layer to a photosensitive layer and a protective layer, and may improve the smoothness of a coating film.

<Image Forming Apparatus>

Next, the image forming apparatus of this embodiment will be described.

7 is a schematic block diagram showing an example of the image forming apparatus of the present embodiment. The image forming apparatus 101 shown in FIG. 7 is provided with the electrophotographic photosensitive member 7 of the drum shape (cylindrical shape) of this embodiment provided rotatably, for example. In the periphery of the electrophotographic photosensitive member 7, for example, along the moving direction of the outer circumferential surface of the electrophotographic photosensitive member 7, the charging device 8, the exposure apparatus 10, the developing apparatus 11, the transfer apparatus 12 ), The cleaning device 13 and the antistatic device (ease device) 14 are arranged in this order. In addition, the cleaning apparatus 13 and the static elimination apparatus (ease apparatus) 14 are arrange | positioned as needed.

- Charging device -

The charging device 8 is connected to a power source 9, a voltage is applied by the power source 9, and charges the surface of the electrophotographic photosensitive member 7.

Examples of the charging device 8 include a contactor-type charger using a conductive charging roller, a charging brush, a charging film, a charging rubber blade, a charging tube, and the like. As the charging device 20, for example, a self-known charger such as a non-contact roller charger, a corotron charger using a corona discharge, or a corotron charger may be used. As the charging device 20, a contact type type charger is preferable.

- Exposure device -

The exposure apparatus 10 exposes the charged electrophotographic photosensitive member 7 to form an electrostatic latent image on the electrophotographic photosensitive member 7.

As the exposure apparatus 10, the optical system apparatus etc. which expose the light, such as a semiconductor laser light, LED light, a liquid crystal shutter light, in an image form on the electrophotographic photosensitive member 10 surface are mentioned, for example. The wavelength of the light source is preferably in the spectral sensitivity region of the electrophotographic photosensitive member 10. As a wavelength of a semiconductor laser, the near-infrared which has an oscillation wavelength before and after 780 nm is good, for example. However, not only this wavelength but a 600 nm wavelength oscillation wavelength laser and a blue laser may also use the laser which has an oscillation wavelength in 400 nm or more and 450 nm or less. Moreover, as the exposure apparatus 30, the surface light-emitting laser light source of the type which multi-beams is output, for example for color image formation is also effective.

- developing device -

The developing device 11 develops a latent electrostatic image with a developer to form a toner image. It is preferable that a developer contains the toner particle of 3 micrometers-9 micrometers of volume average particle diameters obtained by the polymerization method. The developing apparatus 11 may be, for example, a configuration in which a developing roll disposed opposite to the electrophotographic photosensitive member 7 in a developing region is provided in a container containing a two-component developer composed of a toner and a carrier. .

- Transfer device -

The transfer device 12 transfers the toner image developed on the electrophotographic photosensitive member 7 to the transfer medium.

As the transfer device 12, for example, a transfer transfer charger using a belt, a roller, a film, a rubber blade, or the like, a transfer known per se such as a scorotron transfer charger or a corrotron transfer charger using corona discharge, and the like. A charger.

- Cleaning device -

The cleaning apparatus 13 removes the toner remaining on the electrophotographic photosensitive member 7 after transfer.

It is preferable that the cleaning apparatus 13 has the cleaning blade which contacts the electrophotographic photosensitive member 7 at 10 g / cm or more and 150 g / cm or less of linear pressure. The cleaning apparatus 13 is comprised, for example with a casing, a cleaning blade, and the cleaning brush arrange | positioned downstream of the rotation direction of the electrophotographic photosensitive member 7 of a cleaning blade. Further, for example, a solid lubricant is placed in contact with the cleaning brush.

Antistatic Device

The static elimination device (eraise device) 14 irradiates the surface of the electrophotographic photosensitive member 7 after transferring the toner image, thereby eliminating the electric potential remaining on the surface of the electrophotographic photosensitive member. The antistatic device 14 is an exposure part by the exposure apparatus 10 formed on the surface of the electrophotographic photosensitive member 7 by irradiating antistatic light over the entire axial width direction of the electrophotographic photosensitive member 7, for example. And the potential difference between the non-exposed part.

There is no restriction | limiting in particular as a light source of the antistatic device 14, For example, a tungsten lamp (for example, white light), a light emitting diode (LED: for example, red light), etc. are mentioned.

- Fixing device -

The image forming apparatus 100 includes a fixing device 15 for fixing a toner image onto the recording paper P after the transfer process. There is no restriction | limiting in particular as a fixing apparatus, A well-known fixing machine itself, for example, a heat roller fixing machine, oven fixing machine, etc. are mentioned.

Next, the operation of the image forming apparatus 101 according to the present embodiment will be described. First, the electrophotographic photosensitive member 7 rotates along the direction indicated by the arrow A, and is negatively charged by the charging device 8.

The electrophotographic photosensitive member 7 whose surface is negatively charged by the charging device 8 is exposed by the exposure device 10, and an electrostatic latent image is formed on the surface.

When the portion in which the electrostatic latent image is formed in the electrophotographic photosensitive member 7 is close to the developing apparatus 11, the toner image is formed by the developing apparatus 11 to attach toner on the electrostatic latent image.

When the electrophotographic photosensitive member 7 having the toner image formed thereon is further rotated in the direction of the arrow A, the toner image is transferred to the recording paper P by the transfer device 12. As a result, a toner image is formed on the recording paper P. FIG.

In the recording paper P on which an image is formed, a toner image is fixed to the fixing device 15.

<Process Cartridge>

The image forming apparatus according to the present embodiment may be, for example, a form that attaches and detaches the process cartridge including the electrophotographic photosensitive member 7 according to the present embodiment to the image forming apparatus.

The configuration of the process cartridge according to the present embodiment may include at least the electrophotographic photosensitive member 7 according to the present embodiment, and, in addition to the electrophotographic photosensitive member 7, for example, the charging device 8 and the exposure. At least one structural member selected from the apparatus 10, the developing apparatus 11, the transfer apparatus 12, the cleaning apparatus 13, and the static eliminator 14 may be provided.

In addition, the image forming apparatus which concerns on this embodiment is not limited to the said structure, For example, as a periphery of the electrophotographic photosensitive member 7, the rotation direction downstream of the electrophotographic photosensitive member 7 rather than the transfer apparatus 12. The first static elimination device may be provided on the upstream side of the electrophotographic photosensitive member 7 than the cleaning device 13 so as to have the polarity of the remaining toner and to be easily removed by the cleaning brush. Even if the 2nd electrostatic prevention device which static-charges the surface of the electrophotographic photosensitive member 7 is provided in the rotation direction downstream side of the electrophotographic photosensitive member rather than the charging device 8, and the rotation direction upstream of the electrophotographic photosensitive member 7 rather than the charging device 8. do.

In addition, the image forming apparatus according to the present embodiment is not limited to the above-described configuration. After the transfer of the toner image formed on the known configuration, for example, the electrophotographic photosensitive member 7, to the intermediate transfer member, the recording paper ( An image transfer apparatus of an intermediate transfer method that transfers to P) may be employed, or a tandem image forming apparatus may be employed.

In addition, you may apply the electrophotographic photosensitive member which concerns on this embodiment to the image forming apparatus which is not equipped with the antistatic device.

[Example]

Hereinafter, although this invention is demonstrated further more concretely based on an Example and a comparative example, this invention is not limited to a following example at all.

<Example A>

[Production of conductive gas]

(Conductive gas A1)

A slug of JIS-named 1050 alloy having a purity of 99.5% or more of aluminum coated with a lubricant was prepared, and a homogenization treatment was performed at 450 ° C. for 40 minutes. Using the slag subjected to the homogenization treatment, a cylindrical body having a bottom surface is produced by impact pressing by dies and punches, and then ironed. Thus, a cylindrical aluminum base having a diameter of 24 mm, a length of 251 mm, and a thickness of 0.5 mm was produced. Thereafter, an annealing treatment was performed at 220 ° C. for 60 minutes with respect to the aluminum base to obtain a conductive base A1.

The aluminum base obtained through the above process was made into electroconductive base A1.

(Conductive gas A2-A13)

According to Table 1, each conductive base A2-A13 was produced like conductive base A1 except having changed the purity and heat processing conditions of the used aluminum slug. In addition, the dimension of the base was adjusted by changing the impact press working conditions.

However, electroconductive base A9 was obtained by shape | molding the cylindrical molded object by cutting.

[Surface Treatment of Metal Oxide Particles]

(Surface Treatment Example A1)

10 mass% toluene solution of 10 mass% of toluene solution of N-2 (aminoethyl) -3-aminopropyl trimethoxysilane as a metal oxide particle, 100 mass parts of zinc oxide (brand name: MZ-300 Teika Corporation make), and a coupling agent. In addition, 200 mass parts of toluene was mixed and stirred, and reflux was performed for 2 hours. After that, toluene was distilled off under reduced pressure at 10 mmHg, and the baking treatment was performed at 135 ° C for 2 hours.

(Surface Treatment Examples A2 to A3)

Except having changed into the conditions of Table 2, it processed like the surface treatment example 1.

[Example A1]

Formation of Undercoat Layer

Zinc oxide surface-treated in Surface Treatment Example 1: 33 parts by mass, blocked isocyanate semizule 3175 (manufactured by Sumitomo Bio Urethane Co., Ltd.): 6 parts by mass, an electron-accepting compound (example compound (1-6)): 0.7 parts by mass, methyl ethyl Ketone: 25 mass parts are mixed for 30 minutes, and a butyral resin "Esrek BM-1 (made by Sekisui Chemical Co., Ltd.)": 5 mass parts, silicone ball tospur 130 (made by Toshiba Silicone Co., Ltd.): 3 mass parts, leveling Silicone oil "SH29PA" (made by Toray Dow Corning Silicone Co., Ltd.): 0.01 mass part was added, and it disperse | distributed for 2 hours with the sand mill, and obtained the dispersion liquid (coating liquid for undercoat layer formation).

This coating liquid was apply | coated on the electroconductive base A1 by the immersion coating method, 180 degreeC and 30 minutes of dry hardening were formed, and the undercoat layer of 20 micrometers in thickness was further formed.

Formation of charge generating layer

Next, 15 parts by mass of hydroxygallium phthalocyanine was used as the charge generating material, and 10 parts by mass of vinyl chloride-vinyl acetate copolymer resin (VMCH, manufactured by Nihon Union Carbide Co., Ltd.) and 300 parts by mass of n-butyl alcohol. The resulting mixture was dispersed for 4 hours in a sand mill. The obtained dispersion liquid was immersed-coated on the said undercoat layer, and it dried at 100 degreeC for 10 minutes, and formed the charge generation layer of 0.2 micrometer in film thickness.

Formation of charge transport layer

Next, N, N'-diphenyl-N, N'-bis (3-methylphenyl)-[1,1 '] biphenyl-4,4'-diamine: 4 mass parts and bisphenol Z polycarbonate resin (viscosity An average molecular weight of 40,000): 6 parts by mass of tetrahydrofuran: 25 parts by mass and chlorobenzene: 5 parts by mass were added to form a coating solution dissolved on the charge generating layer, followed by drying at 130 ° C. for 40 minutes to achieve a film thickness of 35 μm. A charge transport layer was formed.

The photosensitive member was obtained through the above process.

[Examples A2 to A12, Comparative Example A1]

A photosensitive member was obtained in the same manner as in Example A1 except that the compositions of the conductive substrate and the undercoat layer were changed in accordance with Table 3.

[Evaluation A]

The following evaluation was performed about the photosensitive member obtained by each example.

(Evaluation of conductive gas)

The average area of crystal grains in the conductive base of the photoconductor produced by each example was investigated in accordance with the method described. The results are shown in Table 1 and the like.

(Evaluation of photoreceptor)

Peeling evaluation of the undercoat layer was performed about the photosensitive bodies obtained by each example.

Specifically, peeling evaluation of the undercoat layer was carried out by attaching the photoconductor obtained in each example to Docu Print C1100 manufactured by Fuji Xerox Co., Ltd., and continuously performing A4 paper (Fuji Xerox) in a 10% halftone image at 30 ° C and 85% environment. Co., Ltd., C2 paper), 500,000 sheets of image formation was performed, and visual evaluation was performed on the following reference | standard about peeling of an undercoat layer with an optical microscope. The results are shown in Table 1 and the like.

The evaluation criteria are as follows.

○: good (no peeling)

(Triangle | delta): Although it is slightly behind, there is no problem in actual use (exfoliation occurs out of an image area, but it does not appear on a screen)

×: not available (the peeling occurs on the front)

In Table 1-Table 3, it shows in detail about the detail of an electroconductive base, the detail of the surface treatment of a metal oxide particle, the detail of each Example, and each comparative example.

[Table 1]

[Table 2]

[Table 3]

From the above result, it turns out that peeling of an undercoat layer is suppressed in this Example compared with a comparative example.

<Example B>

[Production of conductive gas]

(Conductive gas B1)

A slug of JIS-named 1050 alloy having a purity of 99.5% or more of aluminum coated with a lubricant was prepared, and a homogenization treatment was performed at 450 ° C. for 40 minutes. Using a slug subjected to the homogenization treatment, a cylindrical body having a bottom surface was produced by impact pressing by a die (shape) and a punch (shape), and then ironed into a diameter of 24 mm, a length of 251 mm, and a thickness. A 0.5 mm cylindrical aluminum substrate was produced. However, the annealing treatment was not performed on the aluminum substrate.

The aluminum base obtained through the above process was made into electroconductive base B1.

The molded object obtained through the above process was made into electroconductive base B1.

(Conductive gas B2-B9)

According to Table 4, each conductive base B2-B9 was produced like conductive base B1 except having changed the purity and heat processing conditions of the used aluminum slug. In addition, the dimension changed and adjusted the impact press working conditions.

Example B1

Formation of Undercoat Layer

Zinc oxide as a metal oxide particle: (average particle diameter: 70 nm: manufactured by Teika Corporation: specific surface area value 15 m 2 / g) 100 parts by mass was stirred and mixed with 500 parts by mass of tetrahydrofuran, and a silane coupling agent (KBM603: Shin-Etsuga Co., Ltd.) was used as the coupling agent. 1.3 mass parts of N-2- (aminoethyl) -3-aminopropyl trimethoxysilane) by the company, was added, and it stirred for 2 hours. Thereafter, toluene was distilled off under reduced pressure, and baking was carried out at 120 ° C. for 3 hours to obtain a silane coupling agent surface treatment zinc oxide.

110 parts by mass of the zinc oxide subjected to the surface treatment was stirred and mixed with 500 parts by mass of tetrahydrofuran, and a solution in which 0.6 parts by mass of alizarin (example compound (1-2)) was dissolved in 50 parts by mass of tetrahydrofuran was added as an electron-accepting compound. It stirred at 50 degreeC for 5 hours. Thereafter, zinc oxide to which alizarin was imparted by filtration under reduced pressure was filtered off, and dried under reduced pressure at 60 ° C to obtain alizarin imparted zinc oxide.

60 parts by mass of this alizarin impregnated zinc oxide and a curing agent (blocked isocyanate semizule 3175, manufactured by Sumitomo Bayer Urethane Co., Ltd.): 13.5 parts by mass and 15 parts by mass of a butyral resin (Esrek BM-1, manufactured by Sekisui Chemical Co., Ltd.) methyl ethyl ketone 85 38 mass parts of the solution melt | dissolved in the mass part and 25 mass parts of methyl ethyl ketones were mixed, it disperse | distributed for 2 hours with the sand mill using the glass bead of 1 mm (phi), and the dispersion liquid was obtained.

Dioctyl tin dilaurate as a catalyst: 0.005 mass part and silicone resin particle (Tospearl 145, GE Toshiba Silicone Co., Ltd.): 40 mass parts was added to the obtained dispersion liquid, and the undercoat layer coating solution was obtained. This coating liquid was applied on an aluminum substrate having a diameter of 30 mm, a length of 340 mm, and a thickness of 1 mm by an immersion coating method, followed by dry curing at 170 ° C. for 40 minutes to form an undercoat having a thickness of 19 μm.

Formation of charge generating layer

Next, the hydroxygallium phthalocyanine having a diffraction peak at a position of at least 7.3 °, 16.0 °, 24.9 °, and 28.0 ° of Bragg angle (2θ ± 0.2 °) of the X-ray diffraction spectrum using Cukα characteristic X-ray as a charge generating material. A mixture consisting of 15 parts by mass, 10 parts by mass of vinyl chloride-vinyl acetate copolymer resin (VMCH, manufactured by Nihon Unica Co., Ltd.) as a binder resin, and 200 parts by mass of n-butyl acetate was used as a side mill using glass beads having a diameter of 1 mmφ. Time was dispersed. 175 mass parts of n-butyl acetate and 180 mass parts of methyl ethyl ketone were added to the obtained dispersion liquid, and it stirred, and obtained the coating liquid for electric charge generation layers. The coating liquid for charge generation layer was immersed and applied on the undercoat layer, and it dried at normal temperature (25 degreeC), and formed the charge generation layer of 0.2 micrometer in film thickness.

Fabrication of charge transport layer

Next, 45 parts by mass of N, N'-diphenyl-N, N'-bis (3-methylphenyl)-[1,1 '] biphenyl-4,4'-diamine and bisphenol Z polycarbonate resin (viscosity average Molecular weight: 50,000) 55 mass parts was added and dissolved in 800 mass parts of chlorobenzene, and the coating liquid for charge transport layers was obtained. This coating liquid was applied onto the charge generating layer, and dried at 130 ° C. for 45 minutes to form a charge transport layer having a film thickness of 20 μm.

[Examples B2 to B16, Comparative Example B1]

A photosensitive member was obtained in the same manner as in Example A1 except that the compositions of the conductive substrate and the undercoat layer were changed in accordance with Table 3.

In addition, titanium oxide (TiO ₂ ) used in Example B5 is TAF500J: (manufactured by Fuji Titanium Co., Ltd.), and tin oxide (SnO) used in Example B6 is S1 Mitsubishi Material Co., Ltd.) to be.

In addition, the coupling agent "KBM573" used in Example B7 is N-phenyl 3-aminopropyl trimethoxysilane (made by Shin-Etsu Chemical Co., Ltd.), and the coupling agent "KBM903" used in Example B8 is 3-aminopropyl tree. It is ethoxysilane (made by Shin-Etsu Chemical Co., Ltd.), and "KBM503" used by Example B16 is 3-methacryloxypropyl trimethoxysilane (made by Shin-Etsu Chemical Co., Ltd.).

[Evaluation B]

The following evaluation was performed about the photosensitive member obtained by each example.

(Evaluation of conductive gas)

The average area of crystal grains in the conductive base of the photoconductor produced by each example was investigated in accordance with the method described. The results are shown in Table 4 and the like.

(Image quality evaluation)

The photoconductors obtained in each example were attached to DocuCentre Color 400CP manufactured by Fuji Xerox Co., and evaluation of image quality deterioration due to the progress of corrosion of the conductive gas was continuously performed under an environment of 30 ° C and 85%.

That is, 500,000 sheets of image formation tests were conducted continuously on an A4 paper (manufactured by Fuji Xerox, C2 paper) on a 10% halftone image at 30 ° C and 85% environment. The density nonuniformity of the 1st image and the image quality dot defect (color point) of the 500,000th image were evaluated. The results are shown in Table 5.

The evaluation criteria of density nonuniformity of image quality and defect of image quality are as follows.

5: There is no image density nonuniformity, or image quality dot defect is not seen at all

4: The image density nonuniformity is seen slightly, or less than three image quality spot defects are seen, but there is no problem in practical use.

3: Although image density nonuniformity is seen, or image quality spot defects are seen more than 3 or less than 5, there is no problem in practical use.

2: The screen is only partially displayed due to the image density unevenness, or five or less to ten image quality point defects are seen.

1: The picture does not come out at all due to the image density unevenness, or image quality point defects are seen in a wide range of 10 or more areas.

(Evaluation of Peeling of Undercoat Layer)

Peeling evaluation of the undercoat layer was performed about the photosensitive bodies obtained by each example.

Specifically, peeling evaluation of the undercoat layer was carried out by attaching the photoconductor obtained in each example to Docu Print C1100 manufactured by Fuji Xerox Co., Ltd. Co., Ltd., C2 paper), and after 500,000 sheets of image formation, visual evaluation was performed on the following reference | standard about the peeling of an undercoat layer with an optical microscope. The results are shown in Table 5 and the like.

The evaluation criteria are as follows.

○: good (no peeling)

(Triangle | delta): Although it is slightly behind, there is no problem in actual use (exfoliation occurs out of an image area, but it does not appear on a screen)

×: not available (the peeling occurs on the front)

In Table 4-Table 5, it shows in detail about the detail of an electroconductive base, the detail of the surface treatment of a metal oxide particle, the detail of each Example, and each comparative example.

[Table 4]

[Table 5]

From the above result, it turns out that peeling of an undercoat layer is suppressed in this Example compared with a comparative example.

Moreover, even if it uses the metal oxide particle surface-treated with the coupling agent which has an amino group from the comparison of Example B1 etc. and Comparative Example B1, corrosion of an electroconductive gas hardly progresses, and about evaluation of the 500,000th quality image point defect It can be seen that good results are obtained. In addition, in Example 16B using metal oxide particles surface-treated with a coupling agent having no amino group, corrosion of the conductive gas is less likely to occur, but the image density unevenness of the first sheet is deteriorated.

1: conductive substrate 2: undercoating layer
3: photosensitive layer 4: intermediate layer
5: protective layer 7: electrophotographic photosensitive member
8: Charging device (an example of charging means) 9: Power supply
10: exposure apparatus (an example of electrostatic latent image forming means)
11: developing device (an example of developing means)
12: transfer device (an example of a transfer means)
13: Cleaning device (an example of cleaning means)
14: antistatic device (an example of antistatic means)
15: fixing device (an example of fixing means) 31: charge generating layer
32: charge transport layer 100, 101: image forming apparatus
P: recording paper (an example of a recording medium)

Claims (17)

A cylindrical conductive base composed of a metal or an alloy and having an average area of crystal grains of 100 µm ² or more,
Photosensitive layer provided on the conductive base
Electrophotographic photosensitive member having a. The method of claim 1,
The electrophotographic photosensitive member whose average area of the said crystal grain of the said electroconductive base is 400 micrometer <^2> or more. The method of claim 1,
The electrophotographic photosensitive member whose average area of the said crystal grain of the said conductive base is 1400 micrometer <^2> or less. The method of claim 1,
An electrophotographic photosensitive member having an undercoat layer provided between the conductive substrate and the photosensitive layer. 5. The method of claim 4,
The electrophotographic photosensitive member in which the said undercoat layer contains the binder resin and the metal oxide particle surface-treated with the coupling agent which has an amino group. The method of claim 1,
The electrophotographic photosensitive member whose thickness of the said electroconductive base is 0.3 mm or more and 0.7 mm or less. The method of claim 1,
The electrophotographic photosensitive member whose thickness of the said electroconductive base is 0.4 mm or more and 0.6 mm or less. The method of claim 1,
The electrophotographic photosensitive member whose metal or alloy which comprises the said conductive base is aluminum or an aluminum alloy. 9. The method of claim 8,
The electrophotographic photosensitive member whose average area of the said crystal grain of the said conductive base is 400 micrometer <^2> or less. 9. The method of claim 8,
The electrophotographic photosensitive member whose average area of the said crystal grain of the said conductive base is 1400 micrometer <^2> or less. 9. The method of claim 8,
An electrophotographic photosensitive member having an undercoat layer provided between the conductive substrate and the photosensitive layer. 12. The method of claim 11,
The electrophotographic photosensitive member in which the said undercoat layer contains the binder resin and the metal oxide particle surface-treated with the coupling agent which has an amino group. 9. The method of claim 8,
The electrophotographic photosensitive member whose thickness of the said electroconductive base is 0.3 mm or more and 0.7 mm or less. 9. The method of claim 8,
The electrophotographic photosensitive member whose thickness of the said electroconductive base is 0.4 mm or more and 0.6 mm or less. 9. The method of claim 8,
The electrophotographic photosensitive member whose content rate of aluminum of the said conductive base is 99.5% or more. The electrophotographic photosensitive member of any one of Claims 1-15 is provided,
A process cartridge detachably attached to an image forming apparatus. The electrophotographic photosensitive member according to any one of claims 1 to 15,
Charging means for charging the surface of the electrophotographic photosensitive member;
Electrostatic latent image forming means for forming an electrostatic latent image on the surface of said electrophotographic photosensitive member,
Developing means for developing a latent electrostatic image formed on the surface of said electrophotographic photosensitive member with toner to form a toner image;
Transfer means for transferring a toner image formed on the surface of the electrophotographic photosensitive member onto a recording medium
An image forming apparatus having a.

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